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Gas-Phase Synthesis of Dimethyl Carbonate from Methanol and Carbon Dioxide Over Co1.5PW12O40 Keggin-Type Heteropolyanion

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Gas-Phase Synthesis of Dimethyl Carbonate from Methanol and Carbon Dioxide Over Co1.5PW12O40 Keggin-Type Heteropolyanion Int. J. Mol. Sci. 2010, 11, 1343-1351; doi:10.3390/ijms11041343 OPEN ACCESS International Journal of Molecular Sciences ISSN 1422-0067 www.mdpi.com/journal/ijms Article Gas-Phase Synthesis of Dimethyl Carbonate from Methanol and Carbon Dioxide Over Co1.5PW12O40 Keggin-Type Heteropolyanion Ahmed Aouissi *, Zeid Abdullah Al-Othman and Amro Al-Amro Department of Chemistry, King Saud University, P.O. Box 2455, Riyadh-11451, Saudi Arabia * Author to whom correspondence should be addressed; E-Mail: [email protected]. Received: 22 January 2010; in revised form: 9 March 2010 / Accepted: 29 March 2010 / Published: 31 March 2010 Abstract: The reactivity of Co1.5PW12O40 in the direct synthesis of dimethyl carbonate (DMC) from CO2 and CH3OH was investigated. The synthesized catalyst has been characterized by means of FTIR, XRD, TG, and DTA and tested in gas phase under atmospheric pressure. The effects of the reaction temperature, time on stream, and methanol weight hourly space velocity (MWHSV) on the conversion and DMC selectivity were investigated. The highest conversion (7.6%) and highest DMC selectivity (86.5%) were obtained at the lowest temperature used (200 °C). Increasing the space velocity MWHSV increased the selectivity of DMC, but decreased the conversion. A gain of 18.4% of DMC selectivity was obtained when the MWHSV was increased from 0.65 h-1 to 3.2 h-1. Keywords: heteropolyanion; Keggin structure; methanol; dimethyl carbonate; direct synthesis; carbon dioxide 1. Introduction Dimethyl carbonate (DMC) has drawn much attention in recent years as an environmentally friendly versatile intermediate. It has been used as a good solvent [1], an alkylation agent [2], and a substitute for highly toxic phosgene and dimethyl sulfate in many chemical processes [3,4]. In addition, it is expected to replace the gasoline oxygenate methyl tert. butyl ether (MTBE), because of its high oxygen content, low toxicity, and rapid biodegradability [1,5,6]. DMC has been produced by the reaction of methanol with phosgene in a concentrated sodium hydroxide solution [7]. However, Int. J. Mol. Sci. 2010, 11 1344 owing to the high toxicity and the severe corrosivity of phosgene, this process has been abandoned gradually. Currently, DMC is produced mainly by oxidative carbonylation of methanol (non-phosgene route) [8]. The synthesis can be carried out in both liquid- and gas-phases. However, both routes use poisonous gas carbon monoxide and there is the possibility of an explosion. Recently, direct synthesis of DMC from CO2 and CH3OH has been reported as a most attractive route due to the low-cost of CO2 and the environmentally benign process [9–14]. However, DMC yield in this route is relatively low due to the fact that CO2 is thermodynamically stable and kinetically inert and due to the deactivation of catalysts induced by water formation in the reaction process [10,15]. Therefore, the development of efficient heterogeneous catalytic systems has attracted more attention. Bian et al. [16] studied the reaction over Cu–Ni/graphite nanocomposite catalyst in gaseous phase. They obtained 10.13% of CH3OH conversion and 89.04% of DMC selectivity at 105 °C. Wu et al. [17] studied the synthesis of DMC from gaseous methanol and CO2 over H3PO4 modified V2O5 catalyst with various molar ratios H3PO4/V2O5 (P/V). The best conversion (1.95%) and selectivity of DMC (92.12%) was obtained at 130 °C on the catalyst H3PO4/V2O5 (P/V = 0.20). Here we report the direct synthesis of DMC from methanol and CO2 in gas phase over Co1.5PW12O40 as a Keggin-type heteropolyanion catalyst. The effect of the reaction temperature, MWHSV, and time on stream on DMC synthesis was investigated. 2. Results and Discussion 2.1. Characterization of Catalysts The FT-IR spectrum of the Co1.5PW12O40 is shown in Figure 1. The IR spectrum has been assigned according to [18,19]. The main characteristic features of the Keggin structure are observed at 1080–1060 cm-1, 990–960 cm-1, 900–870 cm-1, and 810–760 cm-1, assigned to the stretching vibration νas (P-Oa), νas (M-Od), νas (M-Oc-M), and νas (M-Oc-M) , respectively (M = W or Mo). The result of X-ray powder diffraction of the Co1.5PW12O40 salt is shown in Figure 2. In each of the four ranges of 2θ, 7o–10o, 16o–23o, 25o–30o, and 31o–38o, the compound shows a characteristic for well defined Keggin structure of heteropolyanions [20–22]. So the presence of the primary Keggin structure in the synthesized phases was confirmed by FTIR and XRD. Figure 1. IR spectrum of Co1.5PW12O40 Keggin-type heteropolyanion. Int. J. Mol. Sci. 2010, 11 1345 Figure 2. XRD pattern of Co1.5PW12O40 Keggin-type heteropolyanion. Figure 3. Differential thermal analysis (DTA) and thermo-gravimetric analysis (TGA) of Co1.5PW12O40 (heating rate: 5 °C /min). Thermogravimetric (TG) and Dfferential Thermal Analysis (DTA) Thermogravimetric analysis of Co1.5PW12O40 (Figure. 3) showed that the dehydration process starts at low temperature, about 50 °C, and finishes at 250 °C. The differential thermal analysis (DTA) indicates two endothermic peaks below 250 °C, and an exothermic peak at 575 °C. In agreement with the TG results, the endothermic peaks are assigned to the removal of physisorbed or crystallization water molecules (13-14 H2O), whereas the exothermic peak is due to the decomposition of Co1.5PW12O40 into the corresponding oxides (3/2CoO, 12 WO4 and 1/2P2O5). This result is in agreement with published results [23]. 2.2. Catalytic Reaction Int. J. Mol. Sci. 2010, 11 1346 2.2.1. Effect of Reaction Temperature The effect of the reaction temperature on the reaction performance was investigated at temperatures ranging from 200–300 °C. The results are illustrated in Figure 4 and 5. It can be seen from Figure 4 that CH3OH conversion and product yields decreased dramatically with increasing temperature. The decrease of both the conversion and product yields with increasing temperature might be due to the decreased CO2 adsorption on the catalyst at high temperatures [10]. Figure 5 shows that the selectivity of DMC decreased with increasing temperature. The decrease of DMC selectivity is probably due to the decomposition of DMC at higher temperatures [10,16, 24–26]. It can be seen from these results that the highest conversion of 7.6% and highest selectivity of DMC of 86.5% was obtained at the lowest temperature in this range of temperatures (200 °C). Figure 4. The dependence of the conversion and product yields on reaction -1 temperature over Co1.5PW12O40. Reaction conditions: MWHSV = 3.25 h ; molar ratio CH3OH /CO2 = 1.9. 12 Conversion Y(DMC) 10 Y(DMM) Y(MF) 8 6 4 Conversion/Yield (%) 2 0 200 220 240 260 280 300 Temperature (oC) Figure 5. The dependence of the conversion and product selectivity on reaction -1 temperature over Co1.5PW12O40. Reaction conditions: MWHSV = 3.25 h ; molar ratio CH3OH /CO2 = 1.9. Conversion S(DMC) 80 60 40 20 Conversion/Selectivity (%) 0 200 220 240 260 280 300 Reaction temperature (oC) 2.2.2. Effect of Time on Stream Int. J. Mol. Sci. 2010, 11 1347 Figure 6 shows CH3OH conversion and products yield as a function of time on stream. It can be seen that both CH3OH conversion and DMC yield increased rapidly during the first three hours, then after increased slowly. DMM and MF were observed as minor products with a rate formation almost constant. As for the product selectivity, it can be seen from the figure 7 that DMC selectivity increased slightly with increasing time on stream to the detriment of DMM and MF. Figure 6. Time on stream effect on the conversion and product yields. Reaction conditions: -1 T = 200 °C; MWHSV = 3.25 h ; molar ratio CH3OH/CO2 = 1.9. 13 12 11 Conversion 10 Y(DMC) 9 Y(MF+DMM) 8 7 6 5 4 3 Conversion /Conversion Yield (%) 2 1 0 12345 Time on stream (h) Figure 7. The product selectivities as a function of time on stream. Reaction conditions: -1 T = 200 °C; MWHSV = 3.25 h ; molar ratio CH3OH /CO2 = 1.9. 90 80 S(%) 70 60 S(DMC) S(MF+DMM) 50 40 30 20 10 12345 Time on stream (h) 2.2.3. Effect of Space Velocity The effect of methanol weight hourly space velocity (MWHSV) on the conversion of methanol and the selectivity of DMC is shown in Figure 8. It can be seen that the conversion dropped sharply to about 6.4%. In fact, when the SV changed from 0.6 h-1 to 1.6 h-1, the conversion decreased from 15.7% to 9.3%. Further increase of MWHSV did not influence the conversion of methanol considerably. The conversion dropped only to about 1.7%. In fact, it has been found that when the MWHSV changed from 1.6 h-1 to 3.2 h-1, the conversion decreased from 9.3% to 7.6%. As for the selectivity of DMC, the Int. J. Mol. Sci. 2010, 11 1348 result showed that increasing the MWHSV from 0.65 h-1 to 3.2 h-1 increased the selectivity from 68.1% to 86.5% gaining in this way 18.4% of DMC selectivity. Figure 8. Conversion and DMC selectivity over Co1.5PW12O40 as a function of MWHSV. Reaction conditions: T = 200 °C; molar ratio CH3OH /CO2 = 1.9. 90 80 70 60 50 Conversion S(DMC) 40 30 20 Conversion/Selectivity (%) 10 0.5 1.0 1.5 2.0 2.5 3.0 3.5 SV (h-1) 3. Experimental Section 3.1. Catalyst Preparation The heteropolymolybdate salt namely Co1.5PW12O40 was prepared from 12-tungstophosphoric acid H3PW12O40 as precipitate by adding slowly the required amount of CoCO3.
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